Bark or berries of the species Xanthoxylum clavaherculis L and Xanthoxylum americanum Hill, both of the yellow wood tree family, both containing the compound xanthoxylum, are employed for the treatment of hemorrhoids and other membrane and capillary disorders of the veins and arteries. Improved strength and flexibility of the veins, arteries and their constituent structures is obtained.

The present invention relates to a new use of the bark of the prickly ash tree which, more particularly, constitutes a method for the treatment of ailments, such as ailments including, without limitation, hemorrhoids and heart disease.
It has, in the prior art, been known that various plants, herbs, bushes, and the like, will yield certain beneficial medicinal effects. More particularly, and in the context of the instant invention, two types of prickly ash trees have been identified. These, in scientific nomenclature, have been termed Xanthoxylum americanum Mill and the Xanthoxylum clava-herculis L. These plant species are, in the American vernacular, known as the northern prickly ash tree and the southern prickly ash tree. The southern prickly ash is also known as the hercules club prickly ash.
The Merck index of pharmacological agents states that the compound known as xanthoxylum is found in the bark of both the northern and southern prickly ash.
The book "A Guide to Medicinal Plants", by Krochmal, published by Quadrangle Books, indicates that the northern prickly ash (Xanthoxylum americanum Mill) is a shrub or small tree growing from five to ten feet in height. The leaves are alternate and compound, with five to eleven leaflets. The sterns are petioles and are often prickly. The greenish white flower thereof is small and inconspicuous, and its fruit is reddish, globe-shaped, and aromatic. Krochmal also states that alternate names for the northern prickly ash are american prickly ash, common prickly ash, pellitory bark, toothache bush , toothache tree and yellow wood. Said reference further states that the northern prickly ash is found on river banks and in rich moist woods from New England southward to Alabama, Mississippi, Florida, Georgia, Kentucky, West Virginia and Virginia and westward to North Dakota and Oklahoma.
With respect to its usages, Krochmal states that Indians used the bark as a remedy for toothache, and employed a powder of the bark with water to treat colic, rheumatism, and gonorrhea. Said reference also states that the Indians made the bark into a poultice in combination with bear grease for the purpose of treating sores and ulcers. Krochmal further states that Indians applied the bark to infected wounds to draw out fluids. Also, seeds of the northern prickly ash were employed as a remedy for toothache, and the berries were used in cough syrup to induce the coughing of phlegm. Further, Krochmal states that ripe berries were used in hot water to produce a spray for the treatment of mouth sores.
With regard to the southern prickly ash (the Xanthoxylum clava-herculis L.) Krochmal points out that the southern prickly ash is a shrub or small tree which is five to ten feet in height. The leaves are alternate, compound and with five to eleven leaflets. The stems and petioles are often prickly. The flowers are greenish white, small and inconspicuous. The fruit is a reddish globular to elliptic aromatic capsule, with prickles.
Alternate names for the southern prickly ash are the hercules club, pillenterry, sea ash, scrubby prickly ash, string-a-tong, toothache tree, wait-a-bit and wild orange. Krochmal states that the southern prickly ash is found in sand hills, thickets, dry woods, coastal areas, river banks, and sand dunes. Geographically, it is found in Southern Virginia, Kentucky, West Virginia, Louisiana, Arkansas, Alabama, Mississippi, Florida and Oklahoma.
Krochmal also notes that the southern prickly ash was used by the Indians for a wide range of ailments. More particularly, a mixture of the bark with water was used for the treatment of gonorrhea and the bark itself was used as a treatment for toothache. Roots of the southern prickly ash boiled in water were used to induce perspiration. Krochmal further indicates that both Indians and early settlers mixed the inner bark of the southern prickly ash with bear grease and applied it as a poultices to treat ulcers. Also, ripe berries were boiled in hot water to make a spray and blown onto the chest and throat as a treatment for chest ailments. Further, the bark was used for inflammation of the throat.
In addition, the inner bark of the southern prickly ash was boiled in water to produce a lotion for the treatment of various itches. The berries of the prickly ash were considered a tonic, a stimulant, an anti-rheumatic, and effective in the relief of gas, colic, and muscle spasms.
The Merck index indicates that the constituents of xanthoxylum (the active ingredient in prickly ash) include xanthoxylin-N, acrid volatile oil, resin, and tannin.
Volume I of the work entitled a "Hodern Herbal", by Grieve, published by Dover Books, points out that the prickly ash species is a member of a larger botanical family known as the Yellow Wood (Rutaceae) family, all of which possess aromatic and pungent properties. Grieve points out that both the root bark and the berries are used medicinally, and have achieved some official recognition by the mention of the bark and berries thereof in the U.S. Pharmacopoeia. Grieve indicates that the southern prickly ash is believed to be the more medically active of the two species. Further, Grieve states that although the two species are not identical, the respective barks are very similar in terms of the active constituent, namely, xanthoxylum. Also, Grieve indicates that both barks contain small amounts of volatile oil, fat, sugar, gum, acrid, resin, and a bitter alkaloid, believed to be berberine, as well as the above mentioned xanthoxylin which is a colorless, tasteless, crystalline substance which appears in slightly different forms in the bark of the respective species. Grieve further states that the bark of both species yields twelve per cent or more of xanthoxylin. Grieve further states that the northern prickly ash bark exists in commerce and is sold as curved or quilt fragments about 1/24 of one inch (about one millimeter) thick and that the bark of the southern prickly ash is generally sold in 1/12 inch thickness (about two millimeters).
With respect to its medicinal action and usages, Grieve states that the prickly ash has been recommended in the U.S. for chronic rheumatism, typhoid, skin disease and impurity of the blood, and is administered either in the form of a fluid or in dosages of 10 grains (650 milligrams) to 0.5 drams (885 milligrams) in the powdered form, taken three times a day. Grieve goes on to state that the powdered bark forms an excellent application to indolent ulcers and old wounds for cleaning stimulating, drying up and healing such wounds, and that the pulverized bark is used for infections and nervous headaches.
Finally, Grieve states that the berries of the prickly ash are considered even more active that the bark, the berries being carminative and antispasmodic, and are used as an aspirin and for dyspepsia indigestion.
By virtue of the above, it may be appreciated that the bark and berries of species of the prickly ash have been employed in a number of medical applications. However, none of these applications have been concerned with ailments of the vascular system and, more particularly, no use of products of the prickly ash tree has occurred in connection with the treatment of hemorrhoids or cardiovascular disorders. Accordingly the instant invention may be viewed as a new use of a known composition of matter.

Method for the treatment of vascular disorders


Carbon nanotube threads are coated with a coating solution such as dimethylformamide (DMF), ethylene glycol (EG), polyethylene glycol (PEG), PEG200 (PEG with an average molecular weight of approximately 200 grams per mole (g/mol)), PEG400 (PEG with an average molecular weight of approximately 400 g/mol), aminopropyl terminated polydimethylsiloxane (DMS 100 cP),polymide, poly(methylhydrosiloxane), polyalkylene glycol, (3-aminopropyl)trimethoxysilane, hydride functional siloxane O resin, platinum (0) -1,3-divinyl-1,1,3,3-tetramethyl-disiloxane, moisture in air, acetic acid, water, poly(dimethylsiloxane) hydroxy terminated, (3-glycidyloxypropyl)-trimethoxysilane or a combination thereof. The coated carbon nanotubes may be used to stitch in a Z-direction into a composite such as a polymer prepreg to strengthen the composite. The stitching may occur using a sewing machine.

Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. Nanotubes have been constructed with length-to-diameter ratio of up to 132,000,000:1, significantly larger than for any other material. These cylindrical carbon molecules have unusual properties, which are valuable for nanotechnology, electronics, optics and other fields of materials science and technology. In particular, owing to their extraordinary thermal conductivity and mechanical and electrical properties, carbon nanotubes find applications as additives to various structural materials. For instance, nanotubes form a tiny portion of the material(s) in some (primarily carbon fiber) baseball bats, golf clubs, car parts or Damascus steel.

Carbon nanotube thread Z-axis multifunctional stitching


A forwarding database cache system is described herein. The forwarding database cache system includes a main forwarding database and one or more forwarding database caches. When a packet is received, the cache is searched first for information such as address information, and if found, then the packet is forwarded to the appropriate destination. If the address information is not found in the cache, then the main forwarding database is searched, and the packet is forwarded to the appropriate destination based on the information in the main forwarding database.

Cache is a component that transparently stores data so that future requests for that data are able to be served faster. The data that is stored within a cache might be values that have been computed earlier or duplicates of original values that are stored elsewhere. If requested data is contained in the cache (cache hit), this request is able to be served by simply reading the cache, which is comparatively faster. Otherwise (cache miss), the data has to be recomputed or fetched from its original storage location, which is comparatively slower. Hence, the greater the number of requests that can be served from the cache, the faster the overall system performance becomes.

Packet processor forwarding database cache


The present invention relates to a method of arranging user confirmation for data downloading. A request is sent for a description of the object to be downloaded. The description of the object is transmitted, the description comprising an information unit indicating whether user confirmation is required. The information unit is checked. The user is prompted for confirmation in response to the information unit indicating that user confirmation is required. The downloading process of the object is continued in response to the information unit indicating that user confirmation is not required.

OMA (Open Mobile Alliance) has specified procedures for downloading objects, such as files linked to a Web page over the air (OTA) for mobile devices. The OMA download OTA (DLOTA) specification "Generic Content Download Over The Air Specification", version 1.0, 21 Feb. 2003, describes a method for downloading content over the air from a content provider infrastructure to a client (Download Agent). The OMA Download OTA is also referred to as a user-initiated download protocol as the user is able to authorize each download transaction. After a discovery phase (e.g. via browsing), the download agent (DA) downloads a download descriptor file (DD) that contains information about the upcoming media object. The download agent processes the download descriptor file to determine the device capability (available memory or supported media type, for instance) in order to proceed with the download.
The download descriptor also contains the URI (uniform resource identifier) indicating the location from which the media object is going to be downloaded from. However, before accessing such a URI, the user is prompted with a request whether s/he accepts the download or not. If the user accepts to proceed with the OTA transaction, the download agent downloads the media object.
However, the user confirmation for each OTA transaction limits the deployment scenarios of the OMA OTA downloading. It is not possible to arrange downloading which is transparent for the user. For instance, a game, which the user is playing, may require an update file to be downloaded from a game service provider. The user confirmation is prompted in the screen and the user's ongoing game is interrupted. There may be other cases in which the user confirmation represents an unnecessary step for the download transaction.


Improved water resistant acetal sizing agents including 1,1-octadecoxyoctadecane are provided along with methods for their synthesis including methods in which C8 to C30 alkyl bromides are reacted with a polyol under basic conditions and those in which a C8 to C30 primary alcohol is reacted with an organic base in the presence of a suitable oxidizing agent under basic conditions.

The present invention relates generally to sizing compounds, and particularly to compounds used to provide water resistance in the paper and textile industries. Specifically, the invention relates to long chain acetal compounds which are useful as sizing agents and novel methods for their production. A particularly preferred long chain, hydrocarbon-containing compound according to the invention is 1,1-octadecoxyoctadecane, the distearyl acetal of stearyl aldehyde. Further, the invention provides two novel and unexpected methods for synthesizing desired acetal compounds.
The paper industry has now largely converted to alkaline papermaking. The two main reasons for this change are the ability to use calcium carbonate (CaCO3) and the ability to make a stronger and more permanent sheet. A major consequence of this change is that rosin cannot be used as the sizing agent in an alkaline system because rosin must be used with alum and the rosin/alum sizing system does not work at the higher pH range used to make alkane paper. (An exception to this are dispersed rosin sizes which have been used successfully at operating pH ranges as high as 6.5.) To make alkaline paper, the paper industry has turned to the synthetic reactive sizes, ASA (alkenyl succinic anhydride) and AKD (alkyl ketene dimer). These sizing agents work well in an alkaline environment by reacting with the fiber to form a covalent bond between the sizing compound and the hydroxyl groups on the fiber. The major problem with ASA and AKD is that they also react with water to form an insoluble non-sizing material.
ASA is the largest volume sizing agent now used by the paper industry and is the reaction product of an isomerized alpha olefin (with a chain length of C-16 to C-20) and maleic anhydride. The unsaturation and chain lengths of the starting olefin determine the melting point of the ASA (which is usually less than 9xc2x0 C.) and it""s sizing efficiency. Because ASA is an anhydride, it reacts rapidly with the hydroxyl groups on the fiber to form an ester linkage and with water to form a non-sizing hydrolyzate. The rapid reaction of ASA with fiber makes it the most used sizing agent where sizing is needed before the size press to control pickup, but the rapid reaction with water and the resultant non-sizing hydrolyzate, can cause problems for the paper maker such as press roll picking and machine deposits. ASA is not soluble in water and must be emulsified before use. Most ASA is emulsified using high shear emulsification equipment in the presence of a protective colloid such as starch or a synthetic polymer. Cationic starch such as cationic potato starch is most often used because of cost and the ready availability of wet end starch in most mills.
Because hydrolyzed ASA deposits are a major cause of runnability problems many limitations are imposed on its use. Thus, hydrolysis is minimized by using soft water, cooling the starch to room temperature before making down the emulsion and using the emulsion as soon as possible after it is made. If the emulsion must be stored for any length of time, the temperature must be kept low and the pH should be reduced to between 3 and 4. The ASA also must be added as close to the head box as possible to avoid prolonged contact with water. Finally, good first pass retention is critical so that ASA does not get into the white water system where it will hydrolyze and cause runnability problems. To achieve good first pass retention, retention aids should be used and strict attention must be paid to wet end chemistry. Stock pH and dryer settings are important to maximize size efficiency and minimize deposits.
AKD (alkyl ketene dimer) is the other commonly used cellulose reactive alkaline sizing agent but is less preferred than ASA because of its slow on-machine sizing development and higher cost. AKD is much less reactive than ASA, and can be emulsified by the manufacturer and shipped to the mill as a ready to use product. The lactone ring in AKD reacts with the hydroxyl groups on cellulose to form a xcex2-keto ester on the cellulose fibers. Because the AKD is less reactive than ASA, much of the sizing occurs after the dryer section of the paper machine. In some cases, this may be insufficient to control wet end pick-up. AKD reacts with water to form the xcex2-keto acid which rapidly decarboxylates to form the non-sizing, solid ketone. The reaction of AKD with water occurs very slowly at room temperature, such that emulsified AKD has a shelf life of at least a month. AKD sized sheets can also exhibit other problems such as size reversion, excessive sheet slipperiness and fugitive sizing. Like ASA, AKD should be added as close to the head box as possible.
Thus, while sizing agents currently used in the paper industry work well, they all exhibit some deficiencies. ASA""s are very reactive, developing sizing within a few seconds to a few minutes. They are more efficient than rosin, and can be used with alum at pH values as low as 5. However, as ASA""s are readily hydrolyzed, emulsions of these products are not very stable and require in-mill emulsification equipment for preparation. This process can be hard to control and the ASA, being very reactive with water as well as cellulose, can hydrolyze with water before it can react with the fiber leaving machine deposits. AKD""s are less reactive than ASAs and have more stable emulsions, but are also less reactive with cellulose and may require several hours to develop sizing and usually require the concurrent use of a retention aid. Size reversion, fugitive sizing, and machine deposit problems are also encountered. Both AKD and ASA can make the sheet slippery, resulting in problems for users of reprographic paper. ASA and AKD can also contribute to xe2x80x9ctelescopingxe2x80x9d of the paper reel which can lead to converting problems. Rosin is the lowest cost sizing product, but is much less efficient than ASA or AKD as a sizing agent on a per pound basis. Because of this low efficiency, relatively high dosage rates are required, especially when calcium carbonate is used as the filler. Rosin also does not work well at the higher pH range seen under ankaline papermaking conditions.
Of interest to the present invention is the art relating to the synthesis of acetals and ketals. Ordinarily the general preparative method for the synthesis of an acetal or ketal is the acid catalyzed addition of two moles of alcohol to one mole of aldehyde or ketone, with the formation of one mole of acetal or ketal and one mole of water. These reactions are only acid catalyzed and the products are formed by way of a hemiacetal or hemiketal intermediate. If the aldehyde is small, the reaction proceeds favorably. If the aldehyde is large, water must be removed as the material reacts. The reaction in neither direction is catalyzed by base, so most acetals and ketals are quite stable to bases, though they are easily hydrolyzed by acids (March, Advance Organic Chemistry, 4th ed; John Wiley and Sons, New York, 1992, p. 889).
Thus, for simple aldehydes, the overall equilibrium constant is favorable, and the acetal may be prepared simply by treating the aldehyde with two equivalents of alcohol and an acid catalyst. With ketones and larger aldehydes, the equilibrium constant for making the acetal or ketal is generally unfavorable. For most aldehydes, the alcohol can be used as the solvent to drive the equilibrium toward completion. For fatty acetals and ketals, the equilibrium constant is generally unfavorable and water must be removed during the reaction to drive the reaction to completion. Another method to prepare acetals and ketals, particularly fatty acetals and ketals is transacetalation of fatty aldehyde dimethyl acetals and fatty alcohols. (See for example, the disclosure of Mahadevan, Lipids, Vol. 5 (No. 6), pp. 563-565 (1969) which discloses a method for the synthesis of a C-14 acetal of fatty aldehydes and fatty alcohols by transacetalation between fatty aldehyde dimethyl acetals and fatty alcohols.) Acetals and ketals are normally stable to basic conditions, but are easily hydrolyzed back to the aldehyde or ketone and the alcohol under acidic conditions.
There is a need in alkaline papermaking for a sizing agent that works in an alkaline environment and does not hydrolyze in the presence of water. This sizing agent should have a low melting point and should develop some sizing before the size press. This new sizing agent should develop a predictable level of sizing and keep this sizing for the life of the sheet. The new product should be safe and made from readily available materials.
The present invention provides improved acetal sizing compositions and methods for their production. Specifically, the invention provides sizing methods and compositions comprising a dialkyl acetal of a C8-C30 aldehyde and an emulsifying agent. Preferred emulsifying agents include starches and synthetic polymers with cationic starch derivatives being particularly preferred starches. Preferred synthetic polymers include polyacrylamides, polyamides, paper makers alum, and of particular usefulness, the synthetic polymers described in U.S. Pat. No. 4,657,946. Other retention aids may be added to the size emulsion to improve retention of the size in the sheet.
According to a preferred aspect of the invention, the acetal is the dialkyl acetal, 1,1-octadecoxyoctadecane. The sizing composition may be used in a variety of applications including the sizing of substrates selected from the group consisting of paper and textiles and is particularly useful as a wet end size in paper manufacture.
The invention also provides new and improved methods for the synthesis of acetals under basic conditions. Specifically, the invention provides a first method of preparing a dialkyl acetal of a C8 to C30 aldehyde comprising the steps of: (a) reacting a carbohydrate with a base, in alcohol, to produce a caustic treated polyol; and (b) reacting a C8 to C30 alkyl bromide in the presence of the caustic treated polyol of step (a) and a suitable solvent to produce said dialkyl acetal. According to a preferred aspect of the invention the carbohydrate is preferably cellulose which can be in the form of cellulose fibers. The synthesis is carried out under basic conditions with the amount of base in the reaction mixture being controlled by the amount of caustic used to treat the fiber and the amount of said caustic treated fiber used in the reaction mixture. Accordingly, the base to fiber ratio can vary from 1:100 to 2:1 and the alkyl halide to caustic treated fiber ratio can vary from 1:50 to 50:1. Further, according to a preferred aspect of the invention the solvent of step (b) is dimethylsulfoxide (DMSO).
According to a second synthetic method of the invention a dialkyl acetal of a C8 to C30 aldehyde (preferably 1,1-octadecoxyoctadecane) is prepared by a method comprising the step of reacting a C8 to C30 primary alcohol with an organic base in the presence of a suitable oxidizing agent. Preferably, the primary alcohols are C8 to C8 Preferred bases for this reaction include: dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, cyclohexylamine, hexamethylenediamine, methylaniline, dimethylanline, o, m and p-anisidine, o, m and p-phenylenediamine, and o, m and p-toluidine. Diethylamine, triethylanine, n-propylamine, isopropylamine, n-butylamine, sec-butylanine and tert-butylamine are particularly preferred and triethylamine is most preferred. Various oxidizing agents may be used according to the invention with the preferred oxidizing agent being selected from the group consisting of n-chlorosuccinimide, n-bromosuccinimide, sodium hypochlorite and chlorine.
The novel sizing compound of this invention, when used as a paper sizing agent provides more consistent and predictable sizing, does not hydrolyze and leave machine deposits, provides sizing independent of pH and has unlimited shelf life. Moreover, the sizing agents of the invention provide improved waterproofing agents for paper, corrugated board including poultry boxes and milk carton stock, wood products including plywood and particle board, inorganic substrates such as wall board and textile products including those such as outdoor clothing and gear. Preferred fabrics which can be treated with the size so as to render them waterproof include but are not limited to cellulose-containing fabrics such as cotton and rayon. Moreover, the sizing compounds of the invention provide numerous improvements over other compounds currently available including improved durability due to better affinity of the compound to the fiber and greater potential for making the fabric both waterproof and breathable.
The present invention provides improved sizing compounds and new methods for their synthesis. Specifically, the invention provides highly efficient methods for producing long chain acetals under basic conditions without the requirement for water removal during the reaction. A particularly preferred compound for use as a size according to the invention is the acetal 1,1-octadecoxyoctadecane, C54H110O2.
It is anticipated that most carbohydrates will work as the base support (caustic treated polyol) for the reaction of the alkyl halide to the acetal. Cellulose, in the form of wood fiber is the most convenient because it is insoluble in the solvent dimethylsulfoxide (DMSO) and it has the additional advantage of being an excellent carrier for the sizing agent in the wet end of the paper machine. While cellulose is currently preferred as the caustic treated polyol for these reactions, starch, particularly corn and potato starch, may also be used. It has been found, however, that while the reaction works well, the product of the caustic treated starch/alkyl halide reactions is a waxy material that is not as easy to use as the caustic treated cellulose/alkyl halide reaction product. A highly crosslinked starch, particularly if the starch is in the granular form and insoluble in DMSO, should provide a suitable substrate as the base support for these reactions. Using starch as the caustic treated polyol is very desirable because conventional sizing agents as well as those of the present invention, are preferably emulsified with starch before being used as a sizing agent in the paper making system.
The long chain acetals of the invention may be prepared by either of the two inventive methods described herein but may also be produced according to conventional methods known to the art. For example, while the acetal 1,1-octadecoxyoctadecane is preferably produced according to either of the two methods described in the following examples it may also be produced according to the general method described in Mahadevan, Lipids, Vol. 5 (No. 6), pp. 563-565 (1969) or other conventional methods.
The sizing agents of this invention are particularly well suited to the sizing of paper under alkaline conditions due to their unique ability to size the fiber without having to be covalently or ionically bonded to the fiber. The sizing agents of this invention are especially useful to the paper maker because they have a great affinity for carbohydrates, particularly cellulose and most especially wood fibers. The sizing agents of this invention will not hydrolyze in the presence of water or other paper making additives regardless of how long they are left in the system. Sizing material that is not retained on the first pass and gets into the white water system will retain its effectiveness as a size. This is also true for paper that contains the sizing agent that is repulped and added back into the paper making system. The sizing material of the invention which is retained on paper which is recycled in the mill (referred to as xe2x80x9cbrokexe2x80x9d) will not degrade and will retain its effectiveness as a size. While the sizing agents and compositions of the invention can be used in a variety of ways for paper sizing such as with a size press apparatus they have been found to be particularly useful as sizing agents for wet end sizing in the manufacture of paper.
Tests done with handsheets sized with this material have shown no fugitive sizing or size reversion, both of which are common with other sizing compounds, particularly AKD. The sizing agents of this invention, however, do share one characteristic in common with some other sizing agents. Full sizing is not obtained until about 4 hours after the sheets were made. While the degree of cure varies depending on the sample, in general the sheets show an increase in sizing from about 50 to 100%.
The examples of this invention disclose the use of these sizing agents with bleached hardwood and softwood pulps. These pulps are generally believed to be more difficult to size than mechanical pulp. It is expected that they can be used effectively to size any common wood pulp including but not limited to mechanical pulp (stone groundwood, refiner mechanical pulp, thermo-mechanical pulp), chemical-mechanical pulps (chemi-thermo-mechanical pulp, thermo-chemi-mechanical pulp and thermo-mechanical chemi pulp), semichemical pulps (neutral sulfite semichemical, high yield sulfite and high yield kraft pulp), and chemical pulps (kraft, sulfite and soda pulp). The sizing agents of this invention should also work well sizing other cellulose containing materials including but not limited to fiber, thread and fabric made from cotton, rayon, cellulose acetate, flax, jute, straw and hemp.
While examples disclosed have taught the use of straight chain, saturated hydrocarbons to make the novel sizing compounds of this invention, it will be apparent to those skilled in the art that other non-saturated and branched hydrocarbons will work equally as well. Specifically, compounds such as bromooctane, bromononane, bromodecane, bromoundecane, bromododecane, bromotetradecane, bromohexadecane, bromoicosane, 1-bromo-cis-4-octadecene, 1-bromo-cis,cis-9,12-octadecadiene, 1-bromo-4-hexadecyloctadecane, 1-bromo-4-tetradecyloctadecane, 1-bromo-4-hexadecylhexadecane and other saturated, unsaturated and branched long chain alkylbromides could be used in place of or in a mixture with the straight chain alkyl halides to lower the melting point and impart other specific properties to the sizing compound. In addition to bromine, other halogenated compounds could be used in these reactions. Chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorotetradecane, chlorohexadecane, chlorooctadecane, chloroicosane, 1-chloro-cis-4-octadecene, 1-chloro-cis,cis-9,12-octadecadien and other alkyl chlorides being the most common but also including alkyl iodides and alkyl fluorides. Likewise, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexadecanol, icosanol, cis-9-octadecen-1-ol, cis,cis-9,12-octadecadiene-1-ol and other long chain saturated, unsaturated and branched alcohols could be used in place of the straight chain, saturated alcohols to impart or modify specific properties such as the melting point, of the sizing compounds. These are just a few examples of the many compounds that could be used in these reactions that would be apparent to others skilled in the art.
To use the objects of this invention, particularly as paper sizing compounds it is preferred that they be employed in combination with an emulsifier, preferably a cationic material, that also functions as a retention aid. Materials that are commonly used in the paper industry as emulsifying agents are cationic starch derivatives such as those produced from corn, potato, tapioca, and wheat starches and the like. These starches can be primary, secondary, tertiary or quarternary amine starches or other nitrogen containing starch derivatives. While starch is particularly preferred as an emulsifying agent for use in combination with the dialkyl acetal of C8-C30 aldehyde component in practice of the invention, other cationic materials may also be used. Other suitable emulsifying agents include synthetic polymers such as polyacrylamides, polyamides, and of particular usefulness, the synthetic polymers described in U.S. Pat. No. 4,657,946. In addition, components such as paper makers alum may also be used. While these materials, both starches and synthetic polymers are useful individually for the purposes of this invention, they may be combined one with another or with a surfactant to increase their effectiveness.
The sizing agent of the present invention is particularly suitable for uses in applications including paper, fabrics and non-wovens and has properties by which it operates as a one-way valve for water. Specifically, the sizing agents can be applied to substrates including but not limited to diapers, feminine products, incontinence products, umbrellas, raincoats, street clothes, cottons, camping supplies, knapsacks, hats, upholstery, lawn furniture, car seats and trim, work clothes, in tanneries, hospital, surgical and biomedical lab wear for the prevention of absorption of biological-aqueous fluids, tarps and covers. The sizing agents of this invention are further contemplated to be particularly useful for sizing items of clothing such as rain gear such that they will repel aqueous fluids and still remain breathable and comfortable. The novel sizing agents of this invention are also contemplated to be useful for impaling stain rise to aqueous fluids. According to the invention, the sizes may be applied to substrates according to conventional methods at concentrations which can be readily determined by those of skill in the art.
The following Examples are intended to illustrate practice of the preferred embodiments of the invention. Numerous additional embodiments and improvements are apparent upon consideration of the following Examples.

Process for preparing a dialkyl acetal of a C8 to C30 aldehyde